Synthetic closure

ABSTRACT

By achieving an extruded, foamed core formed from plastic material peripherally surrounded and integrally bonded with a cooperating synthetic, plastic, extruded, outer layer, a unique, multi-component, multi-layer synthetic closure is provided which may be employed as a bottle closure or stopper for any desired product, whether the product is a liquid, a viscous material, or a solid distributed in a bottle or container and dispensed through the open portal of the container neck. The present invention achieves a mass producible, resilient, synthetic bottle closure which is employable for any desired bottle, including wine. By employing the present invention, a multi-component or multi-layer synthetic closure is attained which possesses physical properties substantially equal to or better than the physical properties found in cork material, which has caused such cork material to be the principal closure material for wine bottles.

RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 09/176,563, filed Oct. 21, 1998, allowed, which is aContinuation of U.S. Ser. No. 08/932,333, filed Sep. 17, 1997, U.S. Pat.No. 5,904,965, which is a Continuation-in-Part of U.S. patentapplication Ser. No. 08/842,496, filed Apr. 24, 1997 for a SyntheticClosure, now abandoned.

TECHNICAL FIELD

This invention relates to closures or stoppers for containers containingliquids, low viscosity substrates, and small solids, and moreparticularly, to closures or stoppers formed from synthetic materialsand employable as a bottle stopper for a container.

BACKGROUND ART

In view of the wide variety of products that are sold for beingdispensed from containers, particularly containers with round neckswhich define the dispensing portal, numerous constructions have evolvedfor container stoppers or closure means for the portals. Generally,products such as vinegar, vegetable oils, laboratory liquids,detergents, honey, condiments, spices, alcoholic beverages, and thelike, impose similar requirements on the type and construction of theclosure means used for containers for these products. However, wine soldin bottles represents the most demanding product for bottle closuremeans, due to the numerous and burdensome requirements placed upon theclosure means used for wine bottles. In view of these demands, most winebottle closures or stoppers have been produced from a natural materialknown as “cork”.

Although synthetic materials have been proposed for use as wine bottlestoppers or closures, such products have been unable to satisfy all ofthe stringent requirements. As a result, cork has remained the dominantmaterial for wine closures, in spite of the numerous inherent problemsthat exist with cork.

Cork represents the bark of a particular variety of cork oak, quercussuber, a tree of the oak family characteristic of western Mediterraneancountries, such as Portugal, Spain, Algeria, Morocco, France, Italy, andTunisia, that has the ability to renew its bark indefinitely. Cork is avegetable plant comprising tissue made up of dead microcells, generally14-sided polyhedrons, slotting in one against the other, with theintercell space filled with a gaseous mixture, essentially atmosphericair but without the carbon dioxide. It is estimated that 1 cm³ of corknumbers 15 to 40 million hexagonal cells with the thickness of thecellular membranes varying between 1 and 2.5 microns.

The suberose texture is not arranged in a uniform fashion. It iscrisscrossed within its thickness by pores or ducts with walls more orless lignified, forming the lenticels. These are filled with powder of areddish-brown color, rich in tannin. The lenticels are permeable togases and liquids and they are often invaded by molds and othermicroorganisms.

The unevenness, both in membrane thickness and in the height anddiameter of the cell forming the suberose parenchyma, can affect some ofthe cork's mechanical and physical properties, namely itscompressibility and elasticity. The cork oak being able to keep itsphysiological process active at all times, the difference in cell sizeand the thickness of the cellular membrane between cork produced inspring and the succeeding autumn leave discernible rings showing theextent of each year's growth.

The contents of newly formed cells disappear during growth and thesubsequent process of suberization of the membranes, on completion ofwhich all communication with the plant's living tissues ceases. Theuniqueness of quercus suber is the achieved thickness of cork bark, upto several centimeters, which insulates the tree from heat and loss ofmoisture and protects it from damage by animals.

In order to harvest the thick cork bark for the first time, the growthcycle takes between 20 and 30 years, depending on location, weatherconditions etc. yielding the so-called virgin cork. Afterwards, some 10years are needed between each harvest of cork boards or reproductioncork in order to gain the necessary length for some corks. Due to thisprocess, the cork used for the manufacture of bottle closures is areproduction of cork that is formed again after several barking phases.

The properties of cork derive naturally from the structure and chemicalcomposition of the membranes. Because 89.7% of the tissue consists ofgaseous matter, the density of cork is extremely low, about 120 to 200kg/m³, which makes the cork light and a good insulator. Densitydifferences can be explained by the humidity differences, the age andquality of the cork bark and the cork tree and its growth differences.The cellular membranes are very flexible, rendering the cork bothcompressible and elastic. Elasticity enables it to rapidly recover toits original dimensions after any deformation. Its chemical compositiongives the cork the property of repelling moisture. The walls of thecells are crusted with suberin, a complex mixture of fatty acids andheavy organic alcohols.

The value of cork is further increased by its low conductivity of heat,sound and vibration due to the gaseous elements sealed in tiny,impervious compartments. Cork is also remarkably resistant to wear andhas a high friction coefficient, thanks to the honeycomb structure ofthe suberose surface. Cork does not absorb dust and consequently doesnot cause allergies nor pose a risk to asthma sufferers. It is fireresistant, recyclable, environmentally friendly and a renewable product.

These advantages have made natural cork the preferred bottle closure forwine storage, particularly for medium and high quality wines wheretradition, the wine mystique and the bottle opening ritual with acorkscrew, are a very important, though intangible, aspect of the wineconsumption. However, numerous disadvantages of natural cork also existsand derive naturally from the structure and chemical composition of themembranes.

Because cork is a natural product, it is a limited resource. Itslimitations become even more obvious with the following facts: thenatural growing of cork is geographically limited to the westernMediterranean countries; the world wide annual harvest of cork oak barkis 500,000 tons and can barely be increased, because of climatic andecological reasons; and ten-year cycles are needed between each harvestof cork boards. In order to meet the rising worldwide cork demand, thepare cycles of cork have been shortened, leading to inferior qualitiesand constantly rising raw material prices.

The irregularities of the cork's structure due to geographic, climaticand ecological reasons causes many quality variances. This creates acomplex categorization of qualities and standards. Through differenttypes of washing processes, various chemical agents are combined inorder to decontaminate the cork and to treat the appearance of the cork.High quality corks do not need washing. The cork quality is graded,based on the number of lenticels, horizontal and vertical cracks, theirsizes, and other cork specific characteristics. The grading process is asubjective task based on statistically significant populations which isdifficult to perform due to its natural origin, since every cork looks,feels, functions and smells different.

Wine market experts estimate that 1% to 5% of all bottled wine isspoiled by cork taint. At least six chemical compounds have beenassociated with cork taint in wines. Most frequently,2,4,6-trichloranisole (TCA) is the major culprit responsible for theoffensive off-odor and impact on the flavor of the wine. TCA has anextremely low threshold for odor detection. It is detectable atconcentrations as low as 1 ppt or 1.0 nanogram per liter.

In most cases, cork taint does not involve the wine-making process.Typically, the tainting chemical is not found in vineyards or in partsof the winery where the wine is produced. After the wine is bottled, thedefect shows itself, thus spoiling the wine. It is almost exclusivelyassociated with corks.

Also, there is evidence that once the corks have been treated withchlorine, and are brought into interaction with mold fungus throughhumidity, chloranisole is created. Other types of wine spoilage arecaused by oxidation, hydrogen sulfide, volatile acidity, sulfur dioxide,brettanomyces, and mercaptans.

Another problem commonly found with natural cork is leaking bottles.Typically, the lack of tightness between the cork and the neck of thebottle causes 100% to 20% of bottle leakage. However, the majority ofwine leakage is caused by passage of the wine through the cork body.These problems are most often found with lower quality cork material,which is typically porous, too soft, out of round, or out of thepredetermined specifications.

In view of the fact that wine spoilage is caused by oxidation of thewine, any gas exchange between ambient conditions and the interior ofthe wine bottle must be avoided. However, many corks are deformed by thechops or jaws of the bottle corking equipment, which enables airexchange and oxidation to occur. Furthermore, when bottles are stored inan environment where ideal humidity is not maintained, optimumfunctionality of the cork is not achieved and the cork loses itsefficiency as a sealing medium by drying out, becoming brittle and/orlosing its mechanical properties. These problems often cause the cork tobreak when pulled out of the bottle or enable wine spoilage to occur. Inaddition, natural cork absorbs liquids, depending on its structure andquality. This also results in breakage, while the cork is pulled out ofthe bottle.

Further problems or deficiencies found with natural cork is thepropensity of cork worms to store or lay their eggs on the corkmaterial, enabling the larvae to dig gullies into the cork.Consequently, enlarged apertures or channels are formed in the cork,unknown to the bottler, producing unwanted contamination. In addition tothese drawbacks, cork powder and other cork impurities are often able tofall into the wine during the corking process, causing further problemsfor wine bottlers and unwanted surprises for the wine consumer.

In order to avoid some of the difficulties, bottlers have developedvarious coatings, such as paraffins, silicones and polymer materials, inan attempt to ease the movement of the cork into and out of the bottle,as well as to improve the permeability of the cork and fillimperfections in the cork surface. However, no ideal cork coatingproduct has been developed to protect a wine corking member from all ofthe inherent difficulties or drawbacks of the material.

The vast majority of wine-containing bottles are currently being soldwith natural cork stoppers. However, due to the inherent problemsexisting with natural cork, various other products have been developedto close liquid bearing containers, such as wine bottles. These otherclosures principally comprise structural synthetic plastics, crown capmetal stoppers, aluminum caps, plastic caps and combinations thereof.

In spite of these prior art efforts, a universally applicable closurehas not been developed which satisfies all bottlers and consumerrequirements. Particularly, the substantially burdensome requirementsimposed upon closure means used in the wine industry have generally beenemployed as the standard that must be attained by a bottle closure thatwill be accepted by the industry. As a result of these stringentrequirements, these prior art products have been incapable of satisfyingthe requisite needs of the industry.

In particular, one of the principal difficulties to which any bottleclosure is subjected in the wine industry is the manner in which theclosure is inserted into the bottle. Typically, the closure is placed ina jaw clamping member positioned above the bottle portal. The clampingmember incorporates a plurality of separate and independent jaw memberswhich peripherally surround the closure member and are movable relativeto each other to compress the closure member to a diameter substantiallyless than its original diameter. Once the closure member has been fullycompressed, a plunger moves the closure means from the jaws directlyinto the neck of the bottle, where the closure member is capable ofexpanding into engagement with the interior diameter of the bottle neckand portal, thereby sealing the bottle and the contents thereof.

In view of the fact that the jaw members must be independent of eachother and separately movable in order to enable the closure member to becompressed to the substantially reduced diameter, each jaw membercomprises a sharp edge which is brought into direct engagement with theclosure member when the closure member is fully compressed. Dependingupon the composition of the closure member, score lines are frequentlyformed on the outer surface of the closure member, which prevents acomplete, leak-free seal from being created when the closure memberexpands into engagement with the bottle neck.

As a result of this sealing system, closure members other than cork havenot been accepted by the wine industry, due to their inability towithstand this conventional bottling and sealing method. Furthermore,many cork sealing members also incur damage during the bottling process,resulting in leakage or tainted wine.

Another problem inherent in the wine industry is the requirement thatthe wine stopper must be capable of withstanding a substantial pressurebuild up that occurs during the storage of the wine product after it hasbeen bottled and sealed. Due to natural expansion of the wine duringhotter months, pressure builds up, imposing a burden upon the bottlestopper that must be resisted without allowing the stopper to bedisplaced from the bottle. As a result, the bottle stopper employed forwine products must be capable of secure, intimate, frictional engagementwith the bottle neck in order to resist any such pressure build up.

A further problem inherent in the wine industry is the requirement thatsecure, sealed engagement of the stopper with the neck of the bottlemust be achieved virtually immediately after the stopper is insertedinto the neck of the bottle. During normal wine processing, the stopperis compressed, as detailed above, and inserted into the neck of thebottle to enable the stopper to expand in place and seal the bottle.However, such expansion must occur immediately upon insertion into thebottle since many processors tip the bottle onto its side or neck downafter the stopper is inserted into the bottle neck, allowing the bottleto remain stored in this position for extended periods of time. If thestopper is unable to rapidly expand into secure, intimate, frictionalcontact and engagement with the walls of the neck of the bottle, wineleakage will occur.

Therefore, it is a principal object of the present invention to provideclosure means for containers which is manufacturable from syntheticmaterials and effectively closes and seals any desired bottle,container, package and the like.

Another object of the present invention is to provide a syntheticclosure having the characteristic features described above which ismanufacturable on a continuing production basis, thus providing lowermanufacturing costs compared to natural or synthetic (structured)closures and satisfying industry requirements for a removable bottlestopper which is producible substantially more economically than corkclosure/stoppers.

Another object of the present invention is to provide a syntheticclosure having the characteristic features described above which meetsor exceeds all of the requisite physical characteristics found innatural closures or stoppers such as cork.

A further object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described abovewhich is capable of simulating all of the visually aesthetic and tactilecharacteristics found in natural stoppers, such as cork, so as to beeffectively a substitute for cork stoppers or closures for the wineindustry, particularly its ends users in both appearance and feel.

Another object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described abovewhich is capable of being employed in conventional bottling equipmentfor being inserted into a bottle container without experiencing anyunwanted physical damage.

Another object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described abovethat can be substituted for a cork stopper in wine bottles, providingall of the desirable characteristics of conventional cork stoppers whilealso being removable from the bottle in the conventional manner withoutbreaking.

Another object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described above,which is physiologically neutral, capable of being sterilized, as wellas capable of being formed to visually simulate any desiredclassification of natural cork.

A further object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described abovewhich is odorless, remains odorless in position, is tasteless, and onlyabsorbs limited amounts of water.

Another object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described abovewhich is unaffected by diluted acids and bases as well as unaffected bymost oils.

Another object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described abovewhich does not shrink, does not age, does not absorb mold or fungus, andresists damage from insects.

Another object of the present invention is to provide a syntheticclosure or stopper having the characteristic features described abovewhich can be mass produced on a continuing basis and eliminates anyspoilage of wine due to cork taint.

Other and more specific objects will in part be obvious and will in partappear hereinafter.

SUMMARY OF THE INVENTION

By employing the present invention, all of the difficulties anddrawbacks found in the prior art have been completely overcome and amass producible, resilient, synthetic bottle closure is realized byachieving a synthetic, extruded, foamed polymer core peripherallysurrounded and integrally bonded with a cooperating synthetic, extruded,outer layer. The present invention can be employed on any desiredproduct, whether the product is a liquid, a viscous material, or a soliddistributed in a bottle or container and dispensed through the openportal of the container neck.

As will become evident from the following detailed disclosure, themulti-component, multi-layer synthetic closure of the present inventionmay be employed as a bottle closure or stopper for any desired product.However, for the reasons detailed above, wine products impose the mostburdensome standards and requirements on a bottle closure. Consequently,in order to clearly demonstrate the universal applicability of themulti-component/multi-layer synthetic closure of the present invention,the following disclosure focuses on the applicability and usability ofthe multi-component/multi-layer synthetic closure of the presentinvention as a closure or stopper for wine containing bottles. However,this discussion is for exemplary purposes only and is not intended as alimitation of the present invention.

As discussed above, a bottle closure or stopper for wine must be capableof withstanding the pressure build up due to temperature variationsduring storage, as well as preventing any seepage or leakage of the winefrom the bottle. Furthermore, a tight seal must also be established toprevent unwanted gas exchange between ambient conditions and the bottleinterior, so as to prevent any unwanted oxidation or permeation of gasesfrom the wine to the atmosphere. In addition, the unique corkingprocedures employed in the wine industry also impart substantialrestrictions on the bottle closure, requiring a bottle closure which ishighly compressible, has high immediate compression recoverycapabilities and can resist any deleterious effects caused by theclamping jaws of the bottle closure equipment.

Although prior art synthetic products have been produced in an attemptto satisfy the need for alternate bottle closures employable in the wineindustry, such prior art systems have been incapable of meeting all ofthe stringent requirements and demands imposed upon a bottle closure forwine products. However, by employing the present invention, all of theprior art inabilities have been obviated and an effective, easilyemployed, mass-produced synthetic closure has been realized.

The present invention overcomes all of the prior art problems byachieving a multi-component or multi-layer synthetic closure whichpossesses physical properties substantially equal to or better than thephysical properties found in cork material, which has caused such corkmaterial to be the principal closure material for wine bottles. In thepresent invention, the prior art failings have been overcome byachieving a multi-component or multi-layer synthetic bottle closurewhich incorporates a central core member peripherally surrounded by andintegrally bonded to an outer peripheral layer imparting additional,desirable physical characteristics to the effective outer surface of thesynthetic bottle closure. By employing multi-components or multi-layersto form the synthetic bottle closure of the present invention, all ofthe prior art difficulties and drawbacks have been eliminated and aneffective, multi-purpose, easily employed and economically mass producedsynthetic closure is realized.

The multi-component/multi-layer synthetic bottle closure of the presentinvention comprises, as its principal component, the core member whichis formed from extruded, foamed, plastic polymers, copolymers, orhomopolymers. Although any known foamable plastic material can beemployed in the extrusion process for developing the bottle closure ofthe present invention, the plastic material must be selected forproducing physical properties similar to natural cork, so as to becapable of providing a synthetic closure for replacing natural cork as aclosure for wine bottles.

By employing the present invention, a synthetic bottle closure isproduced in a highly automated, high-tech extrusion or molding processwith product tolerances being closely maintained. As a result, variousprior art difficulties encountered with cork products being out of roundor having improper diameters are completely eliminated.

In addition, the multi-component/multi-layer synthetic bottle closure ofthe present invention is manufacturable in any desired color or with anydesired markings or indicia placed on the outer surface thereof.Consequently, if desired, the synthetic bottle closure of the presentinvention may be manufactured with a visual appearance substantiallyidentical to the visual appearance of a cork stopper. In addition to thenatural, wood-grain cork appearance, the synthetic closure of thepresent invention may also be produced with any desired indicia, colors,stripes, logos, etc. formed on the surfaces thereof. These desiredindicia can be formed on either the side or ends of the syntheticclosure of the present invention using conventional printing techniques,embossing techniques, laser printing, laser etching, etc. as known inthe printing industry.

Depending upon the sealing process employed for inserting the syntheticclosure of the present invention in a desired bottle, additives, such asslip additives, may be incorporated into the outer, peripherallysurrounding layer of the synthetic closure of the present invention toprovide lubrication of the synthetic closure during the insertionprocess. In addition, other additives typically employed in the bottlingindustry may also be incorporated into the synthetic closure of thepresent invention for improving the sealing engagement of the syntheticclosure with the bottle as well as reducing the extraction forcesnecessary to remove the synthetic closure from the bottle for openingthe bottle. Furthermore, if desired, a unique combination of additivesselected from the group consisting of antimicrobial agents,antibacterial compounds, and oxygen scavenging materials can beincorporated into the synthetic closure of the present invention inorder to impart unique, heretofore unattainable desirable attributes.

In the present invention, the unique synthetic bottle closure isrealized by forming an outer layer peripherally surrounding the coremember in intimate, bonded, interengagement therewith. The outer,peripheral layer of the synthetic closure is formed from plasticmaterial which is integrally bonded to the cylindrical surface of thecore member by applying the outer layer to the core member by extrusionor molding. However, the outer, peripherally surrounding layer is formedwith a substantially greater density in order to impart the desiredphysical characteristics to the synthetic bottle closure of the presentinvention.

By achieving a multi-component, multi-layer synthetic bottle closure inaccordance with the present invention, a bottle closure is realizedwhich is capable of satisfying all requirements imposed thereon by thewine industry, as well as any other bottle closure/packaging industry.As a result, a synthetic bottle closure is attained that can be employedfor completely sealing and closing any desired bottle for securely andsafely storing the product retained therein.

The invention accordingly comprises an article of manufacture possessingthe features, properties, and relation of elements which will beexemplified in the article hereinafter described, and the scope of theinvention will be indicated in the claims.

BRIEFS DESCRIPTION OF THE DRAWINGS

For a fuller understanding of the nature and objects of the invention,reference should be made to the following detailed description taken inconnection with the accompanying drawings, in which:

FIG. 1 is a perspective view of the multi-component or multi-layersynthetic bottle closure of the present invention;

FIG. 2 is a cross-sectional side elevation view of the multi-componentor multi-layer synthetic bottle closure of the present invention;

FIG. 3 is a test data diagram depicting the effect of temperature onoxygen absorption over time;

FIG. 4 is a test data diagram depicting the effect of humidity on oxygenadsorption over time; and

FIG. 5 is a test data diagram depicting the change in oxygen content inthe wine bottle headspace over time with and without oxygen scavengers.

DETAILED DESCRIPTION

By referring to FIGS. 1 and 2, along with the following detaileddisclosure, the construction of the multi-component or multi-layersynthetic bottle closure of the present invention can best beunderstood. In FIGS. 1 and 2, as well as in the following detaileddisclosure, the multi-component or multi-layer synthetic closure of thepresent invention is depicted and discussed as a bottle closure for wineproducts. However, as detailed above, the present invention isapplicable as a synthetic closure for use in sealing and retaining anydesired product in any desired closure system. However, due to thestringent and difficult demands and requirements placed upon a closurefor wine products, the following detailed disclosure focuses on theapplicability of the synthetic bottle closure of the present inventionas a closure for wine bottles. However, it is to be understood that thisdetailed discussion is provided merely for exemplary purposes and is notintended to limit the present invention to this particular applicationand embodiment.

As shown in FIG. 1, multi-component or multi-layer synthetic bottleclosure 20 comprises a generally cylindrical shape having an outerdiameter larger than the diameter of the portal-forming neck of thebottle into which the closure is to be inserted. In general, the overalldiameter of multi-component, multi-layer synthetic closure 20 isslightly greater than the diameter of the portal into which bottleclosure 20 is to be inserted. In this way, assurance is provided thatsecure sealed contacting interengagement is attained between syntheticclosure 20 and the portal within which it is employed.

As depicted in FIGS. 1 and 2, multi-component/multi-layer syntheticbottle closure 20 comprises core member 22 and peripheral layer 24 whichperipherally surrounds and is integrally bonded to core 22. In thepreferred embodiment, core member 22 comprises a substantiallycylindrically shaped surface 26 terminating with substantially flat endsurfaces 27 and 28.

In the preferred embodiment, surrounding layer 24 is intimately bondeddirectly to core member 22, peripherally surrounding and envelopingsurface 26 of core member 22. Peripheral layer 24 incorporates exposedsurface 30, which comprises a substantially cylindrical shape and formsthe outer surface of multicomponent/multi-layer synthetic bottle closure20 of the present invention, along with flat end surfaces 27 and 28.

In order to assist in assuring entry of synthetic bottle closure 20 intothe portal of the bottle into which closure 20 is inserted, terminatingedge 31 of peripheral layer 24 may be beveled or chamfered. Similarly,terminating edge 32 of peripheral layer 24 also may comprise a similarbevel or chamfer. Although any desired bevel or chamfered configurationcan be employed, such as a radius, curve, or flat surface, it has beenfound that merely cutting ends 31 and 32 with an angle of about 45, thedesired reduced diameter area is provided for achieving the desiredeffect.

By incorporating chamfered or beveled ends 31 and 32 on synthetic bottleclosure 20, automatic self-centering is attained. As a result, whensynthetic bottle closure 20 is compressed and ejected from thecompression jaws into the open bottle for forming the closure thereof,synthetic bottle closure 20 is automatically guided into the bottleopening, even if the clamping jaws are slightly misaligned with theportal of the bottle. By employing this configuration, unwanteddifficulties in inserting bottle closure 20 into any desired bottle areobviated. However, in applications which employ alternate stopperinsertion techniques, chamfering of ends 31 and 32 may not be needed.

In order to produce the attributes required for use in the wineindustry, core 22 is formed from foam plastic material using acontinuous extrusion process. Although other prior art systems haveemployed molded foamed plastic material, these processes have proven tobe more costly and incapable of providing a final product with theattributes of the present invention.

In the preferred embodiment, core member 22 is formed as an extruded,medium or low density closed cell foamed plastic comprising one or moreplastics selected from the group consisting of inert polymers,homopolymers, and copolymers. The preferred plastic material ispreferably selected from the group consisting of polyethylenes,metallocene catalyst polyethylenes, polybutanes, polybutylenes,polyurethanes, silicones, vinyl based resins, thermoplastic elastomer,polyesters, ethylene acrylic copolymers, ethylene-vinyl-acetatecopolymers, ethylene-methyl acrylate copolymers, ethylene-butyl-acrylatecopolymers, ethylene-propylene-rubber, styrene butadiene rubber,ethylene-ethyl-acrylic copolymers, ionomers, polypropylenes, andcopolymers of polypropylene and copolymerizable ethylenicallyunsaturated commoners, as well as ethylenic acrylic copolymers,ethylene-vinyl-acetate copolymers, ethylene-methyl-acrylate copolymers,thermoplastic polyurethanes, thermoplastic olefins, thermoplasticvulcanizates, flexible polyolefins, fluorelastomers, fluoropolymers,polyethylenes, Teflons (polytetrafluoroethylenes),ethylene-butyl-acrylate copolymers, ethylene-propylene-rubber, styrenebutadiene rubber, ethylene-ethyl-acrylic copolymers and blends thereof.Furthermore, if a polyethylene is employed, it has been found that thepolyethylene may comprise one or more polyethylenes selected from thegroup consisting of high density, medium density, low density, linearlow density, ultra high density, and medium low density.

Regardless of the foamable plastic material selected for forming coremember 22, the resulting extruded foam product must have a densityranging between about 100 kg/m³ to 500 kg/m³. Although this densityrange has been found to provide an effective core member, the density ofthe extruded foam core member 20 preferably ranges between about 200kg/m³ to 350 kg/m³.

Since core member 22 is substantially closed cell in structure,additives are intermixed with the plastic material to form a closed cellfoam with minute cells. The resulting core member 22 of the presentinvention has average cell sizes ranging from between about 0.02millimeters to 0.50 millimeters and a cell density ranging between about25,000,000 cells/cm³ to 8,000 cells/cm³. Although this cellconfiguration has been found to produce a highly effective product, ithas been found that the most desirable product possesses an average cellsize ranging between about 0.05 and 0.1 millimeters with a cell densityranging between about 8,000,000 cells/cm³ to 1,000,000 cells/cm³.Furthermore, in order to assure that core member 22 possesses inherentconsistency, stability, functionality and capability of providinglong-term performance, the cell size of core member 22 is homogeneousthroughout its entire length and diameter.

In order to control the cell size of core member 22 and attain thedesired cell size detailed above, a nucleating agent is employed. In thepreferred embodiment, it has been found that by employing a nucleatingagent selected from the group consisting of calcium silicate, talc,clay, titanium oxide, silica, barium sulfate, diamatious earth, andmixtures of citric acid and sodium bicarbonate, the desired cell densityand cell size is achieved.

In this regard, it has been found that cell size and cell density ismost advantageously realized in the formation of core member 22 byemploying between about 0.1 and 5 parts by weight of the nucleatingagent for every 100 parts by weight of the plastic foam. In this way,the desired physical characteristics of core member 22 are realizedalong with the desired control of the cell size and cell density. Thisleads to product consistency currently not available with natural andsynthetic materials.

As is well known in the industry, a blowing agent is employed in formingextruded foam plastic material. In the present invention, a variety ofblowing agents can be employed during the extruded foaming processwhereby core member 22 is produced. Typically, either physical blowingagents or chemical blowing agents are employed. Suitable blowing agentsthat have been found to be efficacious in producing the core member ofthe present invention comprise one or more selected from the groupconsisting of: Aliphatic Hydrocarbons having 1-9 carbon atoms,Halogenated Aliphatic Hydrocarbons having 1-9 carbon atoms and Aliphaticalcohols having 1-3 carbon atoms. Aliphatic Hydrocarbons includeMethane, Ethane, Propane, n-Butane, Isobutane, n-Pentane, Isopentane,Neopentane, and the like. Among Halogenated Hydrocarbons and FluorinatedHydrocarbons they include Methylfluoride, Perfluoromethane, ethylFluoride, 1,1-Difluoroethane (HFC-152a), 1,1,1-Trifluoroethane (HFC430a), 1,1,1,2-Tetrafluoroethane (HFC 134a), Pentafluoroethane,Perfluoroethane, 2,2-Difluoropropane, 1,1,1-Trifluoropropane,Perfluoropropane, Perfluorobutane, Perfluorocyclobutane. PartiallyHydrogenated Chlorocarbon and Chlorofluorocarbons for use in thisinvention include Methyl Chloride, Methylene Chloride, Ethyl Chloride,1,1,1-Trichlorethane, 1,1-Dichloro1-Fluoroethane (HCFC-141b), 1-Chloro1,1-Difluoroethane (HCFC142b), 1,1-Dichloro-2,2,2-Trifluoroethane(HCFC-123) and 1-Chloro-1,2,2,2-Tetrafluoroethane (HCFC124). FullyHalogenated Chlorofluorocarbons include Trichloromonofluoromenthane(CFC11), Dichlorodifluoromenthane (CFC12), Trichlorotrifluoroethane(CFC113), Dichlorotetrafluoroethane (CFC114), Chloroheptafluoropropane,and Dichlorohexafluoropropane. Fully Halogenated Chlorofluorocarbons arenot preferred due to their ozone depiction potential. Aliphatic alcoholsinclude Methanol, Ethanol, n-Propanol and Isopropanol. Suitableinorganic blowing agent is useful in making the foam of the presentinvention include carbon dioxide, nitrogen, carbon, water, air,nitrogen, helium, and argon.

Chemical blowing agents include Azodicarbonamic, Azodiisobutyro-Nitride,Benzenesulfonhydrazide, 4,4-Oxybenzene Sulfonylsemicarbazide, p-TolueneSulfonylsemicarbazide, Barium Azodicarboxlyate,N,N′-Dimethyl-N,N′-Dinitrosoterephthalamide and Trihydrazinotriazine.

Preferably, in order to produce the desired product, the blowing agentis incorporated into the plastic melt in a quantity ranging betweenabout 0.005% to 10% by weight of the weight of the plastic material.

As detailed above, either a physical blowing agent or a chemical blowingagent can be employed as part of the extrusion process for forming coremember 22 of the present invention. However, it has been found that theselection of a physical blowing agent is preferred since physicalblowing agents allow core member 22 of synthetic bottle closure 20 to beachieved with a lower density, which is closer to natural cork.

In this regard, a blowing agent which is inert is preferred. Althoughany desired inert blowing agent may be employed, the blowing agent ispreferably selected from the group consisting of nitrogen, carbondioxides, sulphur dioxide, water, air, nitrogen, helium, and argon. Inaddition, hydrocarbons can be employed as the blowing agent which arepreferably selected from the group consisting of butane, isobutene,pentane, isopentane and propane.

In addition to attaining core member 22 which possesses a constructionwith physical characteristics similar to nature cork, multi-component ormulti-layer synthetic bottle closure 20 of the present invention alsocomprises peripheral layer 24. Peripheral layer 24 is of particularimportance in attaining synthetic bottle closure 20 which is capable ofmeeting and exceeding all of the difficult requirements imposed upon aclosure or stopper for the wine industry.

As discussed above, the wine industry incorporates corking machineswhich incorporate a plurality of cooperating, movable jaws which movesimultaneously to compress the bottle stopper to a diametersubstantially smaller than the diameter of the portal into which thestopper is inserted. Then, once fully compressed, the stopper is forcedout of the jaws directly into the bottle, for expanding and immediatelyclosing and sealing the bottle.

Due to the operation of the cooperating jaws which are employed tocompress the stopper for insertion into the bottle, sharp edges of thejaw members are forced into intimate contact with the outer surface ofthe stopper. Although cork material has been successful in resistingpermanent damage from the jaw edges in most instances, other prior artsynthetic stoppers have been incapable of resisting these cuttingforces. As a result, longitudinal cuts, score lines or slits are formedin the outer surface of the stopper, enabling liquid to seep from theinterior to the exterior of the bottle.

Multi-component/multi-layer synthetic bottle closure 20 of the presentinvention eliminates this inherent problem, existing with prior art corkand synthetic closures, by incorporating peripheral layer 24 whichsurrounds and envelopes substantially the entire outer surface 26 ofcore member 22. In addition, by forming peripheral layer 24 from highdensity, rugged, score-resistant material, synthetic bottle closure 20overcomes all of the prior art difficulties and achieves a bottleclosure having physical properties equal to or superior to conventionalcork material.

In the preferred embodiment, peripheral layer 24 is formed from plasticmaterial identical or similar to the plastic material employed for coremember 22. However, as detailed below, the physical characteristicsimparted to peripheral layer 24 differ substantially from the physicalcharacteristics of core member 22.

In the preferred construction, peripheral layer 24 comprises a thicknessranging between about 0.05 and 5 millimeters and, more preferably,between about 0.1 and 2 millimeters. Although these ranges have beenfound to be efficacious to producing synthetic bottle closure 20 whichis completely functional and achieves all of the desired goals, thepreferred embodiment for wine bottles comprises a thickness of betweenabout 0.1 and 1 millimeter.

In producing peripheral layer 24 and achieving the desired tough, scoreand mar-resistant surface for core member 22, peripheral layer 24preferably comprises a density ranging between about 300 kg/m³ to 1,500kgm³. Most ideally, it has been found that the density of peripherallayer 24 ranges between about 750 kg/m³ to 1,000 kg/m³.

In accordance with the present invention, multi-component or multi-layersynthetic bottle closure 20 of the present invention must be formed withperipheral layer 24 intimately bonded to substantially the entiresurface 26 of core member 22. If any large unbonded areas exist, flowpaths for gas and liquid could result. Consequently, secure, intimate,bonded interengagement of peripheral layer 24 with core member 22 isrequired for attaining a bottle closure for the wine industry.

In order to achieve this integral bonded interconnection betweenperipheral layer 24 and core member 22, peripheral layer 24 is formedabout core member 22 in a manner which assures intimate bondedengagement. Preferably, the desired secure, intimate, bonded,interengagement is attained by simultaneous co-extrusion of core member22 and peripheral layer 24 or by applying peripheral layer 24 to coremember 22 after core member 22 has been formed. By employing eitherprocess, intimate bonded interengagement of peripheral layer 24 to coremember 22 is attained.

By using equipment well known in this industry,multi-component/multi-layer synthetic bottle closure 20 of the presentinvention can be produced by co-extruding core member 22 simultaneouslywith peripheral layer 24 to provide a final product wherein peripherallayer 24 is intimately bonded to core member 22 in a single, continuousoperation. If co-extrusion process is employed, once the continuouselongated co-extruded layers forming synthetic bottle closure 20 havebeen completely formed and are ready for final processing, the elongateddual component material produced is cut to the precise length desiredfor forming synthetic bottle closures 20.

After each bottle closure 20 has been formed with the desired length,the desired chamfer, if needed, is formed at each end of peripherallayer 24 in order to provide the benefits detailed above. Once thechamfer or radius has been achieved, synthetic bottle closure 20 isready for distribution to the desired consumer, unless appropriatecoatings and/or printing will be applied.

In the alternate construction, core member 22 is formed as an elongated,continuous, extruded foam product and is cooled or allowed to cool untilready for subsequent processing. Then, whenever desired, the continuouselongated length forming core member 22 is fed through a cross-headmachine which enables peripheral layer 24 to be formed and positioned inthe desired location peripherally surrounding core member 22 in intimatebonded interengagement therewith. Once the dual component product hasbeen completed, the elongated length of material is cut to the desiredlength for forming bottle closure 20, as detailed above, with thedesired chamfer or radius being formed in peripheral layer 24, attainingthe final product.

In a further alternate embodiment, synthetic bottle closure 20 of thepresent invention is formed by employing generally conventionalinjection molding techniques. As is well known, injection molding is amanufacturing process where plastic is forced into a mold cavity underpressure. The mold cavity is essentially a negative of the part beingproduced, and the cavity is filled with plastic, and the plastic changesphase to a solid, resulting in a positive. Typically, injectionpressures range from 5,000 to 20,000 psi. Because of the high pressuresinvolved, the mold must be clamped shut during injection and cooling.

By employing this process, a plurality of separate and independentbottle closures 20 are simultaneously formed in a multi-cavity moldhaving the precisely desired shape and configuration. Consequently, ifbeveled or chamfered edges are desired, the desired configuration isincorporated into the mold, thereby producing a product with the finalshaped desired.

Typically, injection molding is employed to produce products having asingle composition. However, if desired core member 22 may be formedwith outer peripheral layer 24 surrounding and intimately bonded theretousing alternate techniques such as multi-step molding andmulti-component molds, or subsequent coating operations, such as spraycoating, tumble coating, or immersion coating. By employing theseprocedures, synthetic bottle closures 20 of the present invention areformed in an injection molding process, as desired, achieving theunique, multi-layer, multi-component synthetic bottle closure of thepresent invention.

As discussed above, intimate bonded interengagement of peripheral layer24 to core member 22 is required for providing a synthetic bottleclosure 20 capable of being used in the wine industry. In this regard,although it has been found that the processes detailed above providesecure intimate bonded interengagement of peripheral layer 24 to coremember 22, alternate layers or bonding chemicals can be employed,depending upon the particular materials used for forming core member 22and peripheral layer 24.

If desired, well known bonding agents or tie layers can be employed onthe outer surface of core member 22 in order to provide secure intimatebonded interengagement of peripheral layer 24 therewith. If a tie layeris employed, the tie layer would effectively be interposed between coremember 22 and peripheral layer 24 to provide intimate bondedinterengagement by effectively bonding peripheral layer 24 and coremember 22 to the intermediately positioned tie layer. However,regardless of which process or bonding procedure is employed, all ofthese alternate embodiments are within the scope of the presentinvention, providing a synthetic bottle closure capable of overcomingall of the prior art difficulties and drawbacks.

As detailed above, a wide variety of plastic materials can be employedto produce the extruded multi-component, multi-layer synthetic bottleclosure 20 of the present invention. Although each of the plasticmaterials detailed herein can be employed for both core member 22 andperipheral layer 24, the preferred plastic material for forming bothcore member 22 and peripheral layer 24 comprises one or more selectedfrom the group consisting of medium density polyethylenes, low densitypolyethylenes, metallocene catalyst polyethylenes, polypropylenes,polyesters, ethylene-butyl-acrylate copolymers, vinyl-acetatecopolymers, ethylene-methyl acrylate copolymers, and blends of thesecompounds.

It has also been discovered that the outer peripheral layer or skinlayer 24 may comprise a thermoplastic composition which differs from thethermoplastic composition employed for the core member. In this regard,the outer peripheral layer 24 may comprise one or more selected from thegroup consisting of foamable or non-foamable thermoplasticpolyurethanes, thermoplastic olefins, thermoplastic vulcanizates,flexible polyolefins, fluoroelastomers, fluoro-polymers, polyethylenes,Teflons, and blends thereof. In addition, peripheral layer 24 may beformed from thermoplastic olefinic elastomers such as petrothene TPOE,thermoplastic urethanes thermoplastic polyesters, and other similarproduct formulas.

The particular composition employed for peripheral layer 24 is selectedto withstand the compression forces imposed thereon by the jaws of thecorking machine. However, many different polymers, as detailed above,are able to withstand these forces and, as a result, can be employed forperipheral layer 24. In this regard, one principal feature of thepresent invention is the type of material used for layer 24, as well asthe discovery that a substantially solid, non-foamed or foamedplastic-based outer peripheral layer or skin is securely affixed about afoamed plastic center core, to produce a multi-layer synthetic closurewhich is able to withstand the forces of a cork machine. The ability ofthe present invention to withstand these forces, without productleakage, exists even if cork dust filler is present between the core andthe peripheral layer.

In order to form synthetic bottle closure 20 with all of the desirableinherent physical and chemical properties detailed above, one compoundthat has been found to be most advantageous to employ for outerperipheral layer 24 is metallocene catalyst polyethylene. As detailedbelow, outer peripheral layer 24 may comprise 100% metallocene catalystpolyethylene or, if desired, the metallocene catalyst polyethylene maybe intermixed with a polyethylene. In this regard, it has been foundthat outer peripheral layer 24 preferably comprises between about 25%and 100% by weight based upon the weight of the entire composition ofone or more polyethylenes selected from the group consisting of mediumdensity polyethylenes, medium low density polyethylenes, and low densitypolyethylenes.

In order to demonstrate the efficacy of this embodiment of the presentinvention, a supply of synthetic closures 20 were produced employing100% by weight of metallocene catalyst polyethylene for outer peripherallayer 24. This supply of synthetic bottle closures 20 were identified asSynthetic Closure A and were tested in combination with natural corkbottle closures and synthetic bottle closures 20 in accordance with thepresent invention, using alternative formulations for outer peripherallayer 24. The formulations employed for these comparative samples aredetailed below, along with the test data demonstrating the efficacy ofall of the alternate embodiments of the present invention.

Another formulation which has been found to be highly effective inproviding an outer peripheral layer 24 which meets all of the requiredphysical and chemical attributes to attain a commercially viablesynthetic bottle closure 20 is a polyether-type thermoplasticpolyurethane.

By-employing this material and forming the material in peripheral,surrounding, bonded engagement with any desired foamed core member 22, ahighly effective, multi-layer synthetic closure is attained which isable to meet and exceed all requirements for a wine bottle closure.

In the preferred construction of this embodiment, the particularpolyether-type thermoplastic polyurethane employed for forming outerperipheral layer 24 comprises Elastollan LP9162, manufactured by BASFCorporation of Wyandotte, Mich. As detailed below in the test dataprovided, this compound, referred to as Synthetic Closure B, has beenfound to produce an outer layer in combination with core member 22 whichprovides all of the physical and chemical characteristics required forattaining a highly effective synthetic closure 20 for the wine industry.

In addition to employing the polyether-type thermoplastic polyurethanedetailed above, another compound that has been found to be highlyeffective in providing all of the desirable attributes required forouter peripheral layer 24 is a blend of thermoplastic olefins andthermoplastic vulcanizates. In the preferred embodiment, the blend ofthermoplastic olefins and thermoplastic vulcanizates comprises betweenabout 100% and 90% by weight based upon the weight of the entirecomposition of the thermoplastic olefin and between about 100% and 90%by weight based upon the weight of the entire composition of thethermoplastic vulcanizate. As detailed below in the test data, theconstruction of synthetic closure 20 using an outer peripheral surface24 formed from this blend, referred to below as Synthetic Closure C,provides a wine bottle closure which exceeds all requirements imposedthereon.

Another compound that has also been found to provide a highly effectiveouter peripheral layer 24 for synthetic closure 20 of the presentinvention comprises flexible polyolefins manufactured by HuntsmanCorporation of Salt Lake City, Utah. These compounds are sold under thetrademark REXflex FPO, and comprise homogeneous reactor-synthesizedpolymers, produced under proprietary technology which attains polymershaving unique combinations of properties.

In a further alternate embodiment, a highly effective synthetic bottleclosure 20 is attained by employing metallocene catalyst polyethylenes,either independently or in combination with one selected from the groupconsisting of low density polyethylenes, medium density polyethylenes,and medium low density polyethylenes. In this embodiment, thesematerials are preferably employed for both core member 22 and peripherallayer 24.

Still further additional compounds which have been found to providehighly effective outer peripheral surfaces 24 for forming syntheticbottle closures 20, in accordance with the present invention, compriseTeflon, fluoroelastomeric compounds and fluoropolymers. These compounds,whether employed individually or in combination with each other or withthe other compounds detailed above have been found to be highlyeffective in producing an outer peripheral layer 24 which is capable ofsatisfying all of the inherent requirements for synthetic bottle closure20.

Any of the compounds detailed herein for providing outer peripherallayer 24 can be employed using the extrusion processes detailed above toproduce an outer layer which is securely and integrally bonded to coremember 22, either as a foamed outer layer or a non-foamed outer layer.In addition, these compounds may also be employed using the moldingprocesses detailed above to produce the desired multi-component,multi-layer, synthetic bottle closure 20 of the present invention.

In addition, it has also been found that additives may be incorporatedinto outer peripheral layer 24 in order to further enhance theperformance of the resulting synthetic bottle closure 20. As detailedabove, these additional additives include slip resistant additives,lubricating agents, and sealing compounds.

It has also been discovered that further additional additives may beincorporated into either core member 22 and/or outer layer 24 ofsynthetic closure 20 in order to provide further enhancements anddesirable performance characteristics. These additional additivesincorporate antimicrobial agents, antibacterial compounds, and or oxygenscavenging materials.

The antimicrobial and antibacterial additives are incorporated into thepresent invention to impart an additional degree of confidence that inthe presence of a liquid the potential for microbial or bacterial growthis extremely remote. These additives have a long term time releaseability and further increases the shelf life without further treatmentsby those involved with the bottling of wine. This technology has beenshown to produce short as well as long term results (microbial andbacterial kills in as little as ten minutes with the long termeffectiveness lasting for tens of years) which cannot be achieved with anatural product. An additional additive employed in the presentinvention is an oxygen scavenging system. Since oxygen is the worstenemy for wine, this system will for all intent and purposes eliminatethe possibility of wine oxidation.

Free diatomic oxygen has an antagonistic effect on still wine. Oxidationoccurs over a period of time to render the beverage undrinkable.However, during the bottling process, there is a chance that oxygen istrapped in the headspace between the wine and the closure, oxygen issolublized and released from the wine, and/or oxygen is released from orpermeates through the closure.

In order to reduce the possibility of this oxidation in wine, an oxygenscavenger is incorporated into the synthetic closure to extend andpreserve the freshness and shelf life of the product. Oxygen scavengerconcentrates such as sodium ascorbate, sodium sulfite, edetatedipotassium (dipotassium EDTA), hydroquinone, and similar substances areused to actively bind free oxygen unlike passive barrier layers such asglass and/or barrier polymers. Oxygen residing in the headspace afterbottling and dissolved oxygen in the wine are unaffected by the passivebarriers, but the concentration is reduced in the presence of the oxygenscavengers.

With an oxygen scavenger, the closure system can be designed with bothactive and passive protection from oxidation and result in a prolongedshelf life and an improved wine quality. The oxygen scavengingcapability of the closure remains dormant throughout the bottlingprocess until the mechanism is activated in the presence of moisture.One other major advantage of this oxygen scavenging capability is thepossibility to eliminate the need for vacuum in the headspace beforeclosure insertion; therefore, eliminating one variable in the still winebottling operation.

Oxidation in wine is also expedited by elevated temperatures. Becausethe kinetics of the reaction mechanism of the scavenging system alsoincrease with temperature, closures containing oxygen scavengers provideheightened levels of protection against oxidation. By referring to FIGS.3, 4, and 5, the highly effective, advantageous results attained byemploying an oxygen scavenger in the present invention are fullydetailed.

By employing any desired combination of these agents or additives, afurther enhanced synthetic closure is realized which is capable ofproviding a product performance which has heretofore been incapable ofbeing provided by either cork closures or conventional syntheticclosures.

In order to attain the desired chemical and physical properties formulticomponent/multi-layer synthetic closure 20, core member 22preferably comprises between about 0% and 75% by weight of metallocenecatalyst polyethylene, and between about 25% and 100% by weight of oneor more polyethylenes as detailed above. In forming peripheral layer 24in secure, bonded interengagement therewith, it has been found that anyof the formulations detailed above may be employed, with the selectedformulations being affixed to core member 22 by co-extrusion orcross-head extrusion methods.

In order to demonstrate the efficacy of the present invention, aplurality of samples of multi-component/multi-layer synthetic bottleclosures 20, manufactured in accordance with the present invention, wereproduced and tested. These sample products were produced by employingmetallocene catalyst polyethylene and low density polyethyleneintermixed with each other in the ranges detailed above to form coremember 22. In forming core member 22 of each sample product, the twocompounds were intermixed and formed using conventional foam extrusionequipment. In forming peripheral layer 24, the various compoundsdetailed above were employed to produce alternate embodiments ofsynthetic closure 20 of this invention and identified as SyntheticClosure A, Synthetic Closure B, and Synthetic Closure C. These separateembodiments were each tested and the results thereof are detailed below.

In the forming process, peripheral layer 24 was foamed in the extrusionequipment peripherally surrounding core member 22 and being intimatelybonded thereto. The resulting products were cut in lengths suitable forforming bottle closure 20, followed by a chamfer being formed in edges31 and 32. The resulting closures were then employed in a plurality oftests to prove the ability of the present invention to overcome theprior art difficulties and provide a bottle closure which is equivalentto or better than the properties and performance characteristicsprovided by cork.

In producing the synthetic bottle closure 20 of the present invention inthe manner detailed above, blowing agents and nucleating agents detailedabove were employed as previously disclosed. These additives wereemployed using standard procedures well known in the foam extrusionprocess.

In order to demonstrate the ability of the synthetic bottle closure 20of the present invention to possess physical properties similar to orbetter than natural cork, a comparative analysis of natural cork andsynthetic closure 20 of the present invention was made using the sampleproducts produced as detailed above. By referring to Table I, theability of the synthetic bottle closure 20 of the present invention toachieve physical properties that are equivalent to or better thannatural cork is clearly demonstrated.

TABLE I Property Natural Cork Synthetic Closure Compressive strength 591581 to 15.5 mm radial Max load (LBF) Compressive strength 113.6 126.4 to15.5 mm Radial Max stress (psi) Compressive strength 280.4 300.4 (36%)rectangular Max stress (psi) Compressive recovery 94.79 94.12instantaneous (%) Compressive recovery 98.33 97.88 1 hour (%)Compressive recovery 99.58 98.35 24 hours (%)

In order to demonstrate the ability of the multi-component/multi-layer,synthetic bottle closure of the present invention to meet or exceed thephysical qualities possessed by natural cork when employed as a bottleclosure or stopper for wine, numerous tests were conducted directlycomparing the synthetic bottle closure of the present invention tonatural cork stoppers. However, natural cork varies in quality from anultra low quality to an ultra high quality. Typically, the quality ofthe cork is determined by price in accordance with the followingschedule:

ultra low quality corks are below $90 per 1,000 pieces

low quality natural corks range from $95 to $120 per 1,000 pieces

medium quality natural corks range from $125 to $180 per 1,000 pieces

high quality natural corks range from $175 to $250 per 1,000 pieces

ultra high quality natural corks are above $250 per 1,000 pieces

As detailed below, most test comparisons were made using medium qualitynatural cork. In this regard, since the price for medium quality naturalcork ranges between about $125 to $180 per 1,000 pieces, the samplestested in the following comparisons were made using medium qualitynatural cork found in the highest price range for this category.

Before being used as a test sample, each of the natural cork stopperswere inspected to assure high quality and eliminate obvious flaws thatmight exist. As a result, all of the natural cork stoppers employed inthese tests met the following standards.

Each natural cork stopper was 45 mm in length, 24 mm in diameter and,upon visual inspection, had no visual or functional flaws. Furthermore,natural cork stoppers tested to possess a maximum of three very shallowor narrow lenticels, and were free of dust particles. In addition, thestoppers had no holes or pores in excess of 2 mm, possessed a maximum ofone crack, which was classified as being very tight and less than 8% ofthe cork length. Furthermore, no worm activity was visible, as well asno bellyspots or greenwood. The ends of each cork were relatively cleanand possessed very little chance of chipping on the edges. Finally, nocracks originated from the ends, and growth rings were uniform andsubstantially equidistant.

In conducting the following tests, a supply of synthetic bottle closureof the present invention were manufactured in the manner detailed above.In addition, a separate supply of each different type of natural corkstoppers was established. In conducting each test, a plurality ofsamples were randomly selected from each supply and tested in accordancewith the procedures detailed herein. The results for each test werecomputed and are provided in Tables II, III, IV, and V.

Compression Tests

In this test, the force required to compress each closure or stopperfrom its original diameter to a diameter of 15.5 mm was determined. Inconducting this test, 6 random samples were selected from the supply ofmedium quality natural cork stoppers and six random samples wereselected from the supply of synthetic bottle closures of the presentinvention manufactured in the manner detailed above.

Each sample was separately positioned on a radial compression device,which was installed onto an Instron 1011 Material Tester. Whenpositioned on the radial compression device, each sample was compressedfrom its normal diameter, typically 24.0 mm, to a compressed diameter of15.5 mm. The force value required for compressing each test sample wasrecorded. The overall average resulting force values for each sampletype were computed and are reported in Table II as the maximumcompression force in pounds.

TABLE II Compression Tests Max. Radial Compression CompressionCompression Compression Compression Force to 15/5 mm Recovery RecoveryRecovery Recovery Compression Sample Test (LBF) Instantaneous After 15min. After 1 Hour After 24 Hrs. Set Synthetic Closure A 481.7 94.90%97.45% 97.77% 98.09% 17.49% Natural Cork 483.75 93.86% 96.44% 96.72%  97% 28.78% Medium Quality Synthetic Closure B 398.00  93.5%  97.1% 97.5%  97.7% Synthetic Closure C 329.42  92.2%  95.4%  95.9%  96.3%

Another compression test was conducted to determine the recovery ratefor the closures or stoppers at different time intervals. In conductingthis test, six random samples were selected from the supply of syntheticbottle closures of the present invention, manufactured in the mannerdetailed above, and six random samples were selected from the supply ofmedium quality natural cork closures. This test was designed todetermine the recovery rate for each of the closures after compressionto 13.0 mm and release therefrom.

In conducting this test, each of the selected samples was positioned ina commercially available hand corker having a capability to compress theclosures from their original diameter to a diameter of 13.0 mm, and thenallow each of the stoppers to be released by pushing them out of thecompression jaws with a plunger. In each case, the original diameter ofeach sample was recorded. Thereafter, the diameter of each test samplewas recorded immediately after being ejected from the compression jaws,fifteen minutes after ejection, one hour after ejection, and twenty-fourhours after ejection. The percent recovery for each measurement wascalculated by employing the following formula:${\% \quad \text{Recovery}} = {\frac{Dm}{Do} \times 100}$

where Dm is the measured diameter at the different time interval and Dois the original diameter. The average percent recovers was computed foreach sample type and the results are shown in Table II.

The final compression test conducted was a determination of thecompression set, which is a determination of the ability of each stopperto recover after being exposed to a prolonged 50% linear compression. Inconducting this test, three random samples were selected from the supplyof medium quality natural cork stoppers and three random samples wereselected from the supply of synthetic bottle closures of the presentinvention manufactured in the manner detailed above.

The diameter of each sample was recorded. Then, following the methoddetailed in ASTM Method D-3575 Suffix B, each sample was linearlycompressed to 50% of its original diameter and maintained at thiscompression for 22 hours. The test device consisted of two flat, surfaceground plates capable of securing the samples at the desired 50%compression. At the end of the 22 hours, the samples were allowed torecover for 2 hours, after which the diameter of each sample wasmeasured in the compression direction and the measurements recorded.

The compression set was determined for each sample using the followingformula: Percent Compression Set=100 −[(diameter aftercompression)÷(original diameter) ×100]. The overall average percentcompression set for each sample type was determined by averaging theindividual values calculated for each test sample. This overall averageresult is provided in Table II.

Extraction Force

Another comparative test which was conducted was an extraction forcetest to determine the amount of force required to extract each type ofclosure from a properly corked bottle. In conducting this test, sixrandom samples were selected from the supply of medium quality naturalcorks, and six random samples selected from the supply of syntheticbottle closures of the present invention manufactured in the mannerdetailed above. The device used for testing was an Instron Model 1011Material Tester, which was outfitted with a corkscrew fixture to performthe extraction and measure the forces.

In conducting this test, each of the test samples were inserted into a750 ml bottle filled with water to the 55 mm fill level, using theprocedure described in Practical Aspects of Wine Corkage by Jean MichelRiboulet and Christian Alegoet, Bourgogne Publications, Chaintre,France, pages 148-157. The corkscrew was inserted into the corked bottleand the cork removed, while recording the forces required to extract thecork. For each sample, both the maximum force and the average forcerequired for its extraction was recorded. In Table III, the overallaverage for both the maximum extraction force and the average extractionforce for each sample type is detailed.

TABLE III Extraction Force Maximum Average Extraction Extraction ForceForce Sample Type (lbs) (lbs) Synthetic Closure A 44.50 25.89 NaturalCork - Medium Quality 39.80 23.05 Synthetic Closure B 51.5 25.32Synthetic Closure C 45.083 24.76

Sealing Behavior

The next performance test conducted was a sealing behavior test whichdetermines the ability of the closure or stopper to resist compromisingthe integrity of the seal when the closure is subjected to elevatedpressures inside the bottle. In conducting this test, six random sampleswere selected from the supply of high quality natural corks, six randomsamples were selected from the supply of medium quality natural corks,six random samples were selected from the supply of low quality naturalcorks, and six random samples were selected from the supply of thesynthetic bottle closure of the present invention, manufactured in themanner detailed above. The device used for testing each of the thesamples was a conventional 750 ml bottle, which was modified to allowthe pressure in the bottle to be regulated from 0 psi to 30 psi.

In conducting this test, each sample closure was inserted into a bottleand allowed to recover in the bottle for one hour prior to testing.Thereafter, the samples were inverted and connected to the pressuredevice. The samples were subjected to four elevated pressure levels fortwo-minutes at each level. The pressure levels were 10 psi, 15 psi, 22.5psi and 30 psi. At the end of the two-minute interval at each pressurelevel, each sample was individually observed and rated on the followingscale:

10 =  closure did not move from its original location and no dampnessdetected 8 = closure moved from its original location without pop- pingout of the bottle and no dampness detected 6 = closure did not move fromits original location and dampness was detected, but no dripping 4 =closure moved from its original location without pop- ping out of thebottle and no dampness detected, but no dripping 2 = closure did notmove from its original location and drips 1 = closure moved from itsoriginal location without pop- ping out of the bottle and drips 0 =closure popped out of bottle −40 =    test pressure is lost

The evaluations for each sample were recorded at each interval and theresults for each sample at the four different test intervals weretotalled. Any sample receiving a total score less than 40 was considereda failure. With six closures being tested of each sample type, a totalscore of 240 represented the maximum score attainable and was employedas the standard for passing this test. When fully evaluated, thesynthetic bottle closure A of the present invention, the high qualitynatural cork stoppers, and the medium quality natural cork stoppers allscored 240 points, synthetic bottle closure B and C both scored 260points thereby passing this test. The low quality natural cork stoppersreceived a total point score of 224, resulting in a failure of thistest.

Temperature Test

The next performance test was a temperature test to compare the abilityof the closures to resist any compromising sealing integrity at elevatedtemperatures. In conducting this test, two random samples were selectedfrom the supply of medium quality natural cork and two random sampleswere selected from the synthetic bottle closure of the present inventionmanufactured in the manner detailed above. 750 ml bottles were filledwith water to a level of 55 mm from the bottle lip and 63 mm from thebottle lip. This filling was done in accordance with the disclosurefound in Practical Aspects of Wine Corkage, as detailed above.

Each sample type was inserted into both the 55 mm and 63 mm fill levelsand when sealed in position, the bottle was placed horizontally in anoven at 38 C for twenty-four hours. The samples were observed aftertwenty-four hours for leakage and movement of the closure. Any leakageor movement was considered a failure. The results of this test are shownin Table IV.

TABLE IV 55 mm Fill Level 63 mm Fill Level Sample Leaking MovementLeaking Movement Natural Cork - Fail Pass Fail Pass Medium Quality - 1Natural Cork - Fail Pass Fail Pass Medium Quality - 2 SyntheticClosure - A Pass Fail Pass Pass Synthetic Closure - B Pass Fail PassPass Synthetic Closure - C Pass Fail Pass Pass

Aroma Absorption

In the next performance test, the ability of the closures to resistabsorption of aromas were performed. In this test, eighteen randomsamples were selected from the supply of medium quality natural corksand eighteen random samples were selected from the supply of syntheticbottle closures of the present invention manufactured in the mannerdetailed above. Each of the closures were individually soaked in a whitewine solution for a period of 24 hours. After soaking, each winesolution sample was analyzed for retained odors. The overall resultsrevealed the synthetic closures of the present invention had an aromawhich was described as very consistent, neutral, and light woody. Themedium quality natural cork closures had aromas which were described asvanilla, woody, cardboardy, and papery.

Capillarity

Another test performed on the closures was a capillarity test, which isdesigned to determine the ability of the materials tested to resist theabsorption of red wine above the level of the hydrostatic head of theliquid. In conducting this test, three random samples were selected fromthe supply of medium quality natural cork stoppers and three randomsamples were selected from the supply of synthetic bottle closures ofthe present invention manufactured in the manner detailed above. Thedevice used for testing was a flat-bottom vessel capable of holding redwine at a constant level of 5 mm.

Each of the samples were vertically positioned on the flat-bottom vesselsubmerged in 5 mm of wine for twenty-four hours. Thereafter, the sampleswere removed from the holding tank and blotted dry. Then, the length ofthe wine stain on the exterior of each of the closures was measured andrecorded in millimeters. Due to variations in the rate of absorbencyover the cross-section of the closures, particularly the natural corkclosures, the maximum capillarity or maximum length of the wine stainwas measured as well as the overall average capillarity or wine stainlength. The overall average of each of these results for each of thesample types tested is shown in Table V.

TABLE V Capillarity Maximum Average Sample Capillarity CapillaritySynthetic Closure A 0.00 0.00 Natural Cork - Medium Quality 20.03 6.60Synthetic Closure B 0.00 0.00 Synthetic Closure C 8.0 7.7

Water Absorption

Another test conducted was a water absorption test to compare the amountof water absorbed by each of the sample types. In conducting this test,three random samples were selected from the supply of medium qualitynatural cork stoppers and three random samples were selected from thesynthetic bottle closures of the present invention manufactured in themanner detailed above. The water absorption test conducted was incompliance with ASTM Method D-570. In conducting this test, the deviceused was a water-tight vessel capable of holding enough water tocompletely submerse each sample. The vessel also contained a screen withenough weight to submerge all of the samples simultaneously.

Each sample was weighed to the nearest {fraction (1/10,000)} of a gramand submerged in the tank for 24 hours. Thereafter, the samples wereremoved from the tank and blotted dry. Then, the samples were weighed tothe nearest {fraction (1/10,000)} of a gram and the amount of waterabsorbed determined as the difference between the weight of the samplebefore and after submersion. The water absorption for each sample wascomputed in accordance with the following formula:$\text{Water Absorption} = {\frac{\text{Weight of Water}}{\text{Original Weight of Sample}} \times 100}$

The resulting average absorbency for the synthetic bottle closure A. ofthe present invention was 0.27%, for synthetic closure B.0.215%, and forsynthetic closure C 0.491%, while the average of water absorbency forthe medium quality natural cork stopper was 13.06%.

As is evident from a review of the test results detailed above, themulticomponent/multi-layer synthetic bottle closure of the presentinvention has been clearly demonstrated as possessing physicalcharacteristics which are either equivalent to or better than thephysical characteristics possessed by bottle stoppers formed fromnatural cork. As a result of these test procedures, as well as theforegoing detailed disclosure regarding the synthetic bottle closure ofthe present invention, it is immediately apparent that all of theinherent problems, difficulties, and drawbacks existing with naturalcork stoppers have been completely overcome by the present invention,and a uniform, consistent, easily manufactured and comparativelyinexpensive synthetic bottle closure has been achieved which can beemployed for sealing products in bottles, such as wine, withoutincurring any loss or unwanted change in the physical characteristics ofthe product.

It will thus be seen that the objects set forth above, among those madeapparent from the preceding description, are efficiently attained and,since certain changes may be made in the above article without departingfrom the scope of the invention, it is intended that all mattercontained in the above description or shown in the accompanying drawingsshall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended tocover all of the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which, as amatter of language, might be said to fall therebetween.

Particularly, it is to be understood that the in said claims,ingredients or compounds recited in the singular are intended to includecompatible mixtures of such ingredients wherever the sense permits.

Having described my invention, what I claim is new and desire to secureby Letters Patent is:
 1. A stopper or closure for a product retainingcontainer constructed for being inserted and securely retained in aportal forming neck of the container, said stopper/closure comprising:A. an elongated, cylindrically shaped core member formed from foamedplastic material and comprising terminating end surfaces forming theopposed ends of the cylindrically shaped core member; and B. at leastone layer a. peripherally surrounding and intimately bonded to thecylindrical surface of the core member with the end surfaces of the coremember being devoid of said layer, and b. comprising at least onethermoplastic polymer selected from the group consisting ofpolyethylenes, metallocene catalyst polyethylenes, polybutanes,polybutylenes, polyurethanes, silicones, vinyl-based resins,thermoplastic elastomers, polyesters, ethylenic acrylic copolymers,ethylene-vinyl-acetate copolymers, ethylene-methyl-acrylate copolymers,thermoplastic polyurethanes, thermoplastic olefins, thermoplasticvulcanizates, flexible polyolefins, fluorelastomers, fluoropolymers,polyethylenes, polytetrafluoroethylenes, and blends thereof,ethylene-butyl-acrylate copolymers, ethylene-propylene-rubber, styrenebutadiene rubber, ethylene-ethyl-acrylic copolymers, ionomers,polypropylenes, and copolymers of polypropylene and copolymerizableethylenically unsaturated comonomers; whereby amulti-layer/multi-component synthetic closure is attained which iscapable of completely sealing any desired product in a container,retaining the product in the container for any desired length of timewithout any degradation of the product or degradation of the closure. 2.The synthetic closure/stopper defined in claim 1, wherein thecylindrically shaped core member is further defined as comprisingsubstantially flat terminating surfaces forming the opposed ends of saidcylindrically shaped core member.
 3. The synthetic closure/stopperdefined in claim 1, wherein the plastic material forming the core memberis further defined as comprising medium density or low density, closedcell, foamed plastic comprising one or more selected from the groupconsisting of inert polymers, homopolymers, and copolymers.
 4. Thesynthetic closure/stopper defined in claim 3, wherein said closed cellfoam plastic material is further defined as comprising at least oneselected from the group consisting of polyethylenes, metallocenecatalyst polyethylenes, polybutanes, polybutylenes, polyurethanes,silicones, vinyl-based resins, thermoplastic elastomers, polyesters,ethylenic acrylic copolymers, ethylene-vinyl-acetate copolymers,ethylene-methyl-acrylate copolymers, ethylene-butyl-acrylate copolymers,ethylene-propylene-rubber, styrene butadiene rubber,ethylene-ethyl-acrylic copolymers, ionomers, polypropylenes, andcopolymers of polypropylene and copolymerizable ethylenicallyunsaturated comonomers, as well as ethylenic acrylic copolymers,ethylene-vinyl-acetate copolymers, ethylene-methyl-acrylate copolymers,thermoplastic polyurethanes, thermoplastic olefins, thermoplasticvulcanizates, flexible polyolefins, fluorelastomers, fluoropolymers,polyethylenes, polytetrafluoroethylenes, and blends thereof,ethylene-butyl-acrylate copolymers, ethylene-propylene-rubber, styrenebutadiene rubber, ethylene-ethyl-acrylic copolymers.
 5. The syntheticclosure/stopper defined in claim 3, wherein said closed cell, foamedplastic material is further defined as comprising one or morepolyethylenes selected from the group consisting of high density, mediumdensity, low density, linear low density, ultra high density, and mediumlow density.
 6. The synthetic closure/stopper defined in claim 1,wherein said core member is further defined as comprising a densityranging between about 100 kg/m³ to 500 kg/m³.
 7. The syntheticclosure/stopper defined in claim 6, wherein said core member furthercomprises a density ranging between about 200 kg/m³ to 350 kg/m³.
 8. Thesynthetic closure/stopper defined in claim 6, wherein said core memberis further defined as comprising closed cells having an average cellsize ranging from between about 0.02 millimeters to 0.50 millimeters anda cell density ranging between about 8,000 cells/cm³ to 25,000,000cells/cm³.
 9. The synthetic closure/stopper defined in claim 8, whereinsaid core member is further defined as comprising cell size rangingbetween about 0.05 mm and 0.1 mm and a cell density ranging betweenabout 1,000,000 cells/cm³ to 8,000,000 cells/cm³.
 10. The syntheticclosure/stopper defined in claim 1, wherein said peripheral layer isfurther defined as comprising one or more compounds selected from thegroup consisting of foamable or non-foamable thermoplasticpolyurethanes, thermoplastic olefins, thermoplastic vulcanizates,flexible polyolefins, fluoroelastomers, fluoropolymers, polyethylenes,polytetrafluoroethylenes, and blends thereof.
 11. The syntheticclosure/stopper defined in claim 10, wherein said peripheral layer isfurther defined as comprising one selected from the group consisting offoam plastics and non-foamed plastics.
 12. The synthetic closure/stopperdefined in claim 10, wherein said peripheral layer comprises oneselected from the group consisting of polyether-type polyurethanes,thermoplastic polyolefins, thermoplastic polyvulcanizates, flexiblepolyolefins, and blends thereof.
 13. The synthetic closure/stopperdefined in claim 12, wherein said peripheral layer further comprisesbetween about 10% and 90% by weight based upon the weight of the entirecomposition of a thermoplastic olefin and between about 10% and 90% byweight based upon the weight of the entire composition of athermoplastic vulcanizate.
 14. The synthetic closure/stopper defined inclaim 1, wherein said core member is formed by injection molding. 15.The synthetic closure/stopper defined in claim 14, wherein saidperipheral layer is integrally affixed to the surface of the core memberby employing one process selected from the group consisting of injectionmolding, spray coating, roll coating and bath coating.
 16. The syntheticclosure/stopper defined in claim 15, wherein said peripheral layer isformed in an injection molding die during the formation process for thecore member.
 17. The synthetic closure/stopper defined in claim 1, andfurther comprising at least one additive selected from the groupconsisting of lubricating agents, slip-enhancing compounds,antimicrobial agents, antibacterial agents, and oxygen scavengingcompounds.
 18. The synthetic closure/stopper defined in claim 17,wherein said additives are blended into one selected from the groupconsisting of the core member, the peripheral layer and both the coremember and the peripheral layer.
 19. The synthetic closure/stopperdefined in claim 1, wherein said peripheral layer is further defined ascomprising a thickness ranging between about 0.05 mm and 5 mm.
 20. Thesynthetic closure/stopper defined in claim 19, wherein said peripherallayer is further defined as comprising a thickness ranging between about0.1 mm and 2 mm.
 21. The synthetic closure/stopper defined in claim 1,wherein said peripheral layer is further defined as comprising a tough,score and mar resistant surface and a density ranging between about 300kg/m³ and 1,500 kg/m³.
 22. The synthetic closure/stopper defined inclaim 21, wherein the density of the peripheral layer is further definedas comprising between about 750 kg/m³ and 1,000 kg/m³.
 23. The syntheticclosure/stopper defined in claim 1, wherein the core member and theperipheral layer are both further defined as being formed from one ormore foamable plastic materials selected from the group consisting ofmedium density polyethylenes, low density polyethylenes, metallocenecatalyst polyethylenes, polypropylenes, polyesters,ethylene-butyl-acrylate copolymers, vinyl-acetate copolymers, andethylene-methyl acrylate copolymers.
 24. The synthetic closure/stopperdefined in claim 23, wherein said core member is further defined ascomprising: a. between about 0% and 75% by weight based upon the weightof the entire core member of metallocene catalyst polyethylene, and b.between about 25% and 100% by weight of one or more polyethylenesselected from the group consisting of medium density polyethylenes,medium low density polyethylenes, and low density polyethylenes.
 25. Thesynthetic closure/stopper defined in claim 1 wherein said core memberand said peripheral layer are further defined as being formed byextrusion.
 26. The synthetic closure/stopper defined in claim 25,wherein said core member and said peripheral layer are further definedas being extruded simultaneously.
 27. The synthetic closure/stopperdefined in claim 25, wherein said core member is further defined asbeing extruded separately and subsequent thereto said peripheral layeris formed in extrusion equipment peripherally surrounding and envelopingthe preformed core member.
 28. The synthetic closure/stopper defined inclaim 25, wherein said extrusion process is further defined asincorporating one or more blowing agents selected from the groupconsisting of carbon dioxide, sulphur dioxide, nitrogen, carbon, water,air nitrogen, helium, and argon, Azodicarbonamic Azodiisobutyro-Nitride,Benzenesulfonhydrazide, 4,4-Oxybenzene Sulfonylsemicarbazide, p-TolueneSulfonylsemi-carbazide, Barium Azodicarboxlyate,N,N′-Dimethyl-N,N′-Dinitrosoterephthalamide, Trihydrazinotriazine,Aliphatic Hydrocarbons having 1-9 carbon atoms, Halogenated AliphaticHydrocarbons having 1-9 carbon atoms, Aliphatic Hydrocarbons having 1-9carbon atoms, Aliphatic alcohols having 1-3 carbon atoms and partiallyHydrogenated Chlorocarbon and Chlorofluorocarbons.
 29. The syntheticclosure/stopper defined in claim 28, wherein said blowing agent isfurther defined as comprising between about 0.005% and 10% by weight ofthe weight of the plastic material and comprises an inert blowing agentselected from the group consisting of nitrogen, carbon dioxide,sulphurdioxide, water, air, nitrogen, helium, and argon.
 30. The syntheticclosure/stopper defined in claim 26, wherein a nucleating agent isemployed in the extrusion process and said nucleating agent is selectedfrom the group consisting of calcium silicate, talc, clay, titaniumoxide, silica, barium sulfate, diamatious earth, and mixtures of citricacid and sodium bicarbonate.
 31. The synthetic closure/stopper definedin claim 30, wherein said nucleating agent is further defined ascomprising between about 0.1 and 5 parts by weight for every 100 partsby weight of the plastic material.
 32. The synthetic closure/stopperdefined in claim 1, wherein said peripheral layer is further defined ascomprising indicia formed on the outer surface thereof.
 33. Thesynthetic closure/stopper defined in claim 32, wherein said indiciacomprises one or more selected from the group consisting of letters,symbols, colors, graphics, and wood tones.
 34. A stopper or closure fora product retaining container constructed for being inserted andsecurely retained in a portal forming neck of the container, saidstopper/closure comprising: A. an elongated, solid cylindrically shapedmember dimensioned for insertion in the neck of the fluid productretaining container for closing and sealing the fluid product in thecontainer having terminating end surfaces forming the opposed ends ofthe cylindrically shaped core member, and; B. comprising at least twocomponents concentrically mounted to each other and integrally bondedtogether in the manner which prevents passage of the fluid therebetween;C. said first component comprising an elongated, solid, cylindricallyshaped core member formed from extruded foamed plastic material havingterminating end surfaces forming the opposed ends of the cylindricallyshaped core member, and comprising a density ranging between about 100kg/m³ to 500 kg/m³ and constructed for sealing the fluid productretained in the container and preventing transfer of the fluid productfrom the container prior to removal; and D. said second component a.peripherally surrounding the cylindrical surface of the first componentwith the end surfaces of the core member being devoid of said secondcomponent, b. comprising a thermoplastic polymer in peripheralsurrounding, intimate, bonded engagement with the cylindrical surface ofthe first component and comprising at least one selected from the groupconsisting of polyethylenes, metallocene catalyst polyethylenes,polybutanes, polybutylenes, polyurethanes, silicones, vinyl-basedresins, thermoplastic elastomers, polyesters, ethylenic acryliccopolymers, ethylene-vinyl-acetate copolymers, ethylene-methyl-acrylatecopolymers, thermoplastic polyurethanes, thermoplastic olefins,thermoplastic vulcanizates, flexible polyolefins, fluorelastomers,fluoropolymers, polyethylenes, polytetrafluoroethylenes, and blendsthereof, ethylene-butyl-acrylate copolymers, ethylene-propylene-rubber,styrene butadiene rubber, ethylene-ethyl-acrylic copolymers, ionomers,poly-propylenes, and copolymers of polypropylene and copolymerizableethylenically unsaturated comonomers; and c. having an exposed surfaceconstructed for frictionally engaging a surface of the portal formed inthe neck of the container and being securely engaged therewith untilforcibly removed therefrom, sealing the fluid product in the containerand resisting all forces generated by the fluid product when retained insaid container; whereby a multi-layer/multi-component synthetic closureis attained which is capable of completely sealing any desired fluidproduct in a container, retaining the product in the container for anydesired length of time without any degradation of the fluid product ordegradation of the closure.
 35. The synthetic closure/stopper defined inclaim 34, wherein the cylindrically shaped core member is furtherdefined as comprising substantially flat terminating surfaces formingthe opposed ends of said cylindrically shaped core member.
 36. Thesynthetic closure/stopper defined in claim 34, wherein the plasticmaterial forming the core member is defined as comprising medium densityor low density, closed cell, foamed plastic comprising one or moreselected from the group consisting of inert polymers, homopolymers, andcopolymers.
 37. The synthetic closure/stopper defined in claim 36,wherein said closed cell foam plastic material is further defined ascomprising at least one selected from the group consisting ofpolyethylenes, metallocene catalyst polyethylenes, polybutanes,polybutylenes, polyurethanes, silicones, vinyl-based resins,thermoplastic elastomers, polyesters, ethylenic acrylic copolymers,ethylene-vinyl-acetate copolymers, ethylene-methyl-acrylate copolymers,ethylene-butyl-acrylate copolymers, ethylene-propylene-rubber, styrenebutadiene rubber, ethylene-ethyl-acrylic copolymers, ionomers,polypropylenes, and copolymers of polypropylene and copolymerizableethylenically unsaturated comonomers as well as ethylenic acryliccopolymers, ethylene-vinyl-acetate copolymers, ethylene-methyl-acrylatecopolymers, thermoplastic polyurethanes, thermoplastic olefins,thermoplastic vulcanizates, flexible polyolefins, fluorelastomers,fluoropolymers, polyethylenes, polytetrafluoroethyles,ethylene-butyl-acrylate copolymers, ethylene-propylene-rubber, styrenebutadiene rubber, ethylene-ethyl-acrylic copolymers and blends thereof.38. The synthetic closure/stopper defined in claim 36, wherein saidclosed cell, foamed plastic material is further defined as comprisingone or more polyethylenes selected from the group consisting of highdensity, medium density, low density, linear low density, ultra highdensity, and medium low density.
 39. The synthetic closure/stopperdefined in claim 34, wherein said peripheral layer is further defined ascomprising one or more compounds selected from the group consisting offoamable or non-foamable thermoplastic polyurethanes, thermoplasticolefins, thermoplastic vulcanizates, flexible polyolefins,fluoroelastomers, fluoropolymers, polyethylenes, polytetrafluoroethyles,and blends thereof.
 40. The synthetic closure/stopper defined in claim39, wherein said peripheral layer is further defined as comprising oneselected from the group consisting of foam plastics and non-foamedplastics.
 41. The synthetic closure/stopper defined in claim 39, whereinsaid peripheral layer comprises one selected from the group consistingof polyether-type polyurethanes, thermoplastic polyolefins,thermoplastic polyvulcanizates, flexible polyolefins, and blendsthereof.
 42. The synthetic closure/stopper defined in claim 41, whereinsaid peripheral layer further comprises between about 10% and 90% byweight based upon the weight of the entire composition of athermoplastic olefin and between about 10% and 90% by weight based uponthe weight of the entire composition of a thermoplastic vulcanizate. 43.The synthetic closure/stopper defined in claim 34, wherein saidperipheral layer is further defined as comprising a thickness rangingbetween about 0.05 mm and 5 mm.
 44. The synthetic closure/stopperdefined in claim 43, wherein said peripheral layer is further defined ascomprising a thickness ranging between about 0.1 mm and 2 mm.
 45. Thesynthetic closure/stopper defined in claim 34, wherein said peripherallayer is further defined as comprising a tough, score and mar resistantsurface and a density ranging between about 300 kg/m³ and 1,500 kg/m³.46. The synthetic closure/stopper defined in claim 45, wherein thedensity of the peripheral surface is further defined as comprisingbetween about 750 kg/m³ and 1,000 kg/m³.
 47. A stopper or closure for awine-retaining container constructed for being inserted and securelyretained in a portal forming neck of the container, said stopper/closurecomprising: A. an elongated, solid, cylindrically shaped memberdimensioned for insertion in the portal of the neck of the wineretaining container for closing and sealing the wine in the container;B. comprising two components concentrically mounted to each other andintegrally bonded together in a manner which prevents passage of anyfluid therebetween; C. said first component comprising an elongated,solid, cylindrically shaped core portion formed from extruded foamedplastic material having substantially at terminating end surfacesforming the opposed ends of the cylindrically shaped core portion,comprising a density ranging between about 100 kg/m³ and 500 kg/m³ andconstructed for sealing the wine retained in the container andpreventing transfer of the wine and any gases produced thereby out ofthe container prior to removal thereof; and D. said second component a.peripherally surrounding the cylindrical surface of the fist componentwith the substantially flat end surface of the core portion being devoidof any second component, b. comprising a thermoplastic polymer formed inperipheral surrounding, intimate, bonded engagement with the cylindricalsurface of the first component comprising at least one selected from thegroup consisting of polyethylenes, metallocene catalyst polyethylenes,polybutanes, polybutylenes, polyurethanes, silicones, vinyl-basedresins, thermoplastic elastomers, polyesters, ethylenic acryliccopolymers, ethylene-vinyl-acetate copolymers, ethylene-methyl-acrylatecopolymers, thermoplastic polyurethanes, thermoplastic olefins,thermoplastic vulcanizates, flexible polyolefins, fluorelastomers,fluoropolymers, polyethylenes, polytetrafluoroethylenes, and blendsthereof, ethylene-butyl-acrylate copolymers, ethylene-propylene-rubber,styrene butadiene rubber, ethylene-ethyl-acrylic copolymers, ionomers,polypropylenes, and copolymers of polypropylene and copolymerizableethylenically unsaturated comonomers, c. having a density rangingbetween about 300 kg/m³ and 1,500 kg/m³, and d. having an exposedsurface comprising a tough, score and mar resistant construction forresisting the compressive force of a corking machine employed forinserting the closure/stopper into the portal of a wine retainingbottle, and constructed for frictionally engaging a surface of theportal formed in the neck of the container and being securely engagedtherewith until forcibly removed therefrom, sealing the wine in thecontainer and resisting all forces generated by the wine retained insaid container.
 48. The synthetic closure/stopper defined in claim 47,wherein said peripheral layer is defined as being formed from extrudedplastic material comprising one selected from the group consisting offoamed plastics and non-foamed plastics.